Surface and Coatings Technology 150 (2002) 246–256

Electrolytic plasma processing for cleaning and metal-coating of steel

surfaces
E.I. Meletis, X. Nie*, F.L. Wang, J.C. Jiang
Materials Science and Engineering Program, Mechanical Engineering Department, Louisiana State University, Baton Rouge, LA 70803, USA

Received 2 May 2001; accepted in revised form 8 September 2001

Abstract

Electrolytic plasma processing (EPP) involves electrolysis and electrical discharge phenomena and it is an emerging,
environmentally friendly surface engineering technology. Electrolytic-plasmaymaterial surface interactions during processing can
be used for cleaning of metal surfaces, formation of diffusion layers andyor deposition of metal, ceramic and composite coatings.
The present work was concerned with cleaning and deposition of metal coatings on steel surfaces for corrosion protection. The
effects of processing parameters on (i) cleaning steel surfaces (oxides and contamination); and (ii) Zn and Zn – Al coating
deposition were investigated. Surface roughness and oxygen content prior to and after cleaning were evaluated by profilometry
and energy dispersive X-ray analysis (EDAX), respectively. The structure of the EPP cleaned outer surface layer as it evolves
after the electrolytic – plasma interaction was studied by high resolution TEM. Morphology, microstructure, composition, adhesion
and density of EPP-deposited Zn and Zn – Al coatings on cleaned surfaces were studied as a function of processing parameters.
Corrosion properties of the cleaned and coated steels were evaluated by corrosion potential and potentiodynamic polarization
measurements. The results show that EPP can effectively produce clean surfaces and also metal and alloy coatings at high
deposition rates, and it has a great potential as a new plasma surface engineering technique. 䊚 2002 Elsevier Science B.V. All
rights reserved.

Keywords: Corrosion; Cleaning; Coating; Zn; Zn – Al; Plasma electrolysis

1. Introduction
Metallic coatings (such as zinc and zinc–aluminum)
can provide corrosion protection to the base metal from
a corrosive environment by acting as sacrificial anodes
(cathodic protection). Such protection requires a more
active corrosion potential for the coating compared to
the substrate material. Under these conditions, the coat-
ing corrodes preferentially and provides protection to
base metal even when exposed due to coating disconti-
nuities or mechanical damage. Corrosion tests and data
of a zinc protective coating for steel have been devel-
oped and widely used to describe its performance w1,2x.
In the majority of applications for structural steel
(ship and marine structures, pipelines, bridge supports,
industrial structures, etc.), cleaning is required prior to
coating of the surface. Cleaning is needed firstly because
steel is covered by a layer of mill-scale (produced by
* Corresponding author: Tel.: q1-225-578-5808; fax: q1-225-
578-5924.
E-mail address: xnie1@lsu.edu (X. Nie).
the hot-rolling mill), other ‘soil’ and oil and grease
contamination. Secondly, adhesion to base metal is of
utmost importance to coating performance and is directly
related to the cleanliness of the surface and the ability
to develop an ‘anchor’ surface profile (surface with
microscale roughness) providing a key or mechanical
interlocking for the coating.
Traditional methods of cleaning steel include: acid
pickling and sandyshotygrit blasting. These convention-
al methods have major disadvantages (high energy cost,
environmentally-unfriendly, disposal problems, unfavor-
able surface profile, etc.). Electrolytic cleaning methods
are known, but they have not been successfully com-
mercialized since in their present state they are unable
to remove mill-scale and other heavy contaminants.
Likewise, current metal coating methods have several
limitations. For example, electro- and electroless plating
are relatively slow and may use environmentally hazard-
ous chemicals. Dipping and metal spraying methods are
faster but the resulting coatings may have adhesion
problems during bending and formation in some cases.

0257-8972/02/$ - see front matter 䊚 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 2 5 7 - 8 9 7 2 Ž 0 1 . 0 1 5 2 1 - 3
 E.I. Meletis et al. / Surface and Coatings Technology 150 (2002) 246–256
Thus, there is a need at present for new, cost-effective
cleaning and coating methods that can produce quality,
long-lasting surfaces.
Plasma electrolysis is a relatively new surface engi-
neering technique, which includes an anodic process
(such as plasma electrolytic anodic oxidation) w3,4x and
a cathodic process (such as plasma electrolytic satura-
tion) w5x. Plasma electrolysis has a similar configuration
to a conventional anodic oxidation or electroplating
process. However, the applied electrode potential in all
the electrolytic plasma processes is much higher than
that of the conventional processes. The bi-phase
electrodeyelectrolyte system normally encountered in
conventional electrolysis is transformed into a four-phase
electrodeydielectricygas(plasma)yelectrolyte couple for
the anodic oxidation processing or a three-phase
electrodeygas(plasma)yelectrolyte couple for the
cathodic processing w6x. In the plasma discharge
channelyarea, plasma chemical interaction occurs, and
oxides w3,4x or nitrides w5x can form on substrate
surfaces to be treated.
Plasma electrolysis can be quite versatile. For exam-
ple, it can be utilized in conjunction with PVDyCVD
processes for improvement of tribological and corrosion
properties w4x, or with electrophoresis to form biomedi-
cal ceramic coatings w7x. In this work, plasma electrol-
ysis was extended to cleaning mill-scales on steel
surfaces, and to depositing Zn and Al–Zn coatings on
steel substrates as well, for the purpose of corrosion
protection.
Electrolytic plasma process (EPP) may have the
potential to overcome limitations of conventional meth-
ods, both for the cleaning and metal-coating of steel
w8,9x. In the present work, EPP was studied in relation
to cleaning steel surfaces and developing zinc (Zn) and
zinc–aluminum (Zn–Al) coatings.
2. Process description
Electrolytic plasma processing involves two charac-
teristic phenomena (i) electrolysis of a liquid environ-
ment by application of different electrical potentials
between the workpiece material and a counter-electrode;
and (ii) the production of an electrical discharge at, or
in the vicinity of, the workpiece surface. Although the
discharge phenomena associated with electrolysis were
discovered more than a century ago by Sluginov w10x,
their importance as an emerging surface engineering
process were realized only very recently w11x. A typical
electrode current–voltage characteristic curve of the
electrolytic cathodic process is shown in Fig. 1. The
normal glow discharge zone U2 –U29 –U3 is usually
selected as the work region, where the electrode current
decreases but plasma intensity increases when the elec-
trode voltage increases from U2 to U29. The samples (as
a cathode) can be either immersed in the electrolyte
247
(Fig. 1a), or dripped with electrolyte (Fig. 1b). How-
ever, the corresponding slope of the electrode current–
voltage curve in the U2 –U29 segment is different in
these two cases. For the configuration shown in Fig. 1a
(i.e. the workpiece is immersed in the electrolyte), the
current sharply drops from the highest point to the
lowest point when the electrode voltage increases from
U2 to U29. For the configuration in Fig. 1b (i.e. in this
case, the electrolyte drips down to the workpiece through
small diameter holes on the cathodic electrode plate),
the slope of the U2 –U29 line (i.e. current reduction rate)
is much smaller than that of Fig. 1a. It is found that the
plasma intensity increases when electrode voltage
increases, and when U29 is reached, a continuous enve-
lope is formed on the sample surface, which results in
rapid increase of the surface temperature with increasing
electrode voltage. The normal operation voltage in this
work is within U2 –U29. Although there is heating of the
substrate due to plasma action, the bulk substrate tem-
perature remains relatively low (less than 200–3008C)
due to the simultaneous cooling action by the electrolyte
solution. The local surface temperature adjacent to
plasma bubbles, however, is very high, which is critical
to cleaning mill-scale and enhancing the metallurgical
connection of the coating microstructure.
There appears to be several distinct physical processes
involved in cleaning and subsequent coating using EPP
w8,9,12x. While the electrolyte flows through the perfo-
rated anode onto the workpiece (cathode) (Fig. 2), a
potential is applied across the electrode gap and sets up
a strong electric field. The hydrogen evolution reaction
begins to occur at the surface of the workpiece, creating
fine hydrogen bubbles. A strong electrical potential is
established on the bubble adjacent to the workpiece
surface, and hydrogen plasma is thus generated in a thin
layer, just above the steel surface. Metal cations present
in the electrolyte film begin to migrate toward the steel
surface, but the large majority of these ions are attached
to the hydrogen bubbles. These ions are either original
additions to the electrolyte or are generated from the
anode metal by electrolytic decomposition.
In particular, in the case of cleaning, the cations may
be sodium (i.e. sodium carbonate solution) which will
participate in the process but ultimately remain in
solution. The ions due to adsorption gradually concen-
trate on the hydrogen bubble surface and the bubble is
thus converted into a small capacitor. The electrical
field between the positive ions at the bubble surface and
the negatively charged steel surface ionizes the hydrogen
gas in the bubble, resulting in a high temperature plasma.
This occurs quickly once hydrogen starts forming. The
lifespan of the average hydrogen bubble is less than 1
ms and the plasma exists for 1–10 ms w8,11x. The
plasma is continuously forming at this high rate over
the entire steel surface. The nature of the plasma bulb
generation and extinction results in local surface melting
248 E.I. Meletis et al. / Surface and Coatings Technology 150 (2002) 246–256
Fig. 1. Current – voltage dependence in electrolytic plasma discharge.
and also creates forceful pressure disruptions at the
surface associated with bubble collapsing and shock
wave production. The net effect of these processes is
the removal andyor reduction of the milling-scale at the
steel surface and the formation of circular wavelets and
spheroids. Also, the freezing that follows local melting
causes a quenching effect that may result in ultra fine
grained (or even amorphous) structures, as shown later
in this work.
In the coating process, some metal ions may find
their way to the steel surface by diffusion through the
electrolyte but the predominant modes of transport are
ion acceleration through the plasma and ion bubble
adsorption transport where ions are carried to the steel
surface by riding the surface of the hydrogen bubble as
it collapses. Both of the latter processes eliminate the
boundary layer diffusion and result in high deposition
rates.
3. Experimental
The present work involved characterization and study
of corrosion behavior of surfaces and coatings cleaned
and deposited, respectively, by EPP. Low carbon steel
(AISI 1010) was selected as the substrate material. A
laboratory unit was utilized to produce the aforemen-
tioned cleaned surfaces and coatings according to the
processing conditions shown in Table 1. These condi-
tions were selected based on previous experience with
EPP and the desire to systematically study the effect of
processing parameters on the characteristics of the
cleaned surfaces and produced coatings. Zn coatings
were produced under two different process arrange-
ments. In the first, a stainless steel anode was used and
Zn deposition occurred entirely from the electrolyte (Zn
coating I) and in the second, a Zn anode was utilized
thus Zn was deposited from the electrolyte and the
anode (Zn coating II).
After processing, specimen surfaces were examined
by scanning electron microscopy (SEM) to characterize
the surface morphology. The microstructure of the outer
surface layer evolved by the electrolytic–plasma inter-
action was studied by focused ion beam (FIB) methods
w13x and high resolution transmission electron micros-
copy (TEM) (JEOL 2010) on cross-sections of EPP
cleaned surfaces. Metallographic cross-sections were
also prepared to determine coating thickness, density
and uniformity. Density was assessed by taking micro-
hardness measurements (Knoop at 10 gf) on coating
cross-sections. Energy dispersive X-ray analysis
(EDAX) was conducted in conjunction with SEM (Hita-
chi S 4500) to analyze the composition prior to and
after EPP cleaning. Wavelength dispersive spectroscopy
(Jeol JXA 733 super electron probe microscope) was
conducted (at 15 keV accelerated voltage and 10 nA
beam current) to analyze Zn and Al content in the Zn–
 E.I. Meletis et al. / Surface and Coatings Technology 150 (2002) 246–256 249

Fig. 2. Schematic illustration of the electrolytic plasma process.

Al coatings. Profilometry was performed after process-
ing to characterize surface topography. Coating adhesion
was determined by pull tests. Tapered Al pins (2.7-mm
head diameter) were bonded to the coating with an
epoxy (cured at 1508C for 30 min). The adhesion
strength was estimated from the force required to pull
the pin from the specimen.
Corrosion potential measurements and anodic polari-
zation tests were performed to characterize the general
corrosion behavior of the clean steel surfaces as pro-
duced by EPP. Tests were also conducted on the back-
ground low carbon steel (cleaned by grinding with 600
grit paper) for comparison purposes. Anodic polarization
tests were also carried out on the Zn and Zn–Al coatings
produced by EPP. Such tests were also performed on
hot-dip galvanized steel (denoted as: galvanized) spec-
imens that were supplied by the International Lead Zinc
Organization (ILZRO).
The first type of experiments involved corrosion
potential measurements for clean steel and background
steel as a function of time in tap water for a total
duration of 8=104 s. The second type of experiments
involved anodic polarization scans that were conducted
for all surfaces and coatings in two different environ-
ments: tap water and 3.5% NaCl solution using an
EG&G Corrosion Measurement System (Model 273).
In these tests, the potential was first allowed to stabilize
and then scanned from a value of approximately 200–
300 mV below the open circuit potential (OCP) to a
value of approximately 800 mV above OCP at the scan
rate of 0.2 mV sy1, while current was continuously
recorded. The corrosion rate was calculated from these
tests using the Tafel extrapolation method. All corrosion
potentials were measured with respect to a saturated
calomel electrode (SCE).
4. Results and discussion
4.1. Effect of processing parameters
The processing parameters used for the EPP cleaning
and coating treatments are listed in Table 1. The EPP
cleaned surfaces were characterized in terms of surface
morphology, roughness and oxygen content. The char-
acteristics of the cleaned surface with the lowest oxygen
content are presented in Table 2. Similarly, coatings
were assessed in terms of adhesion, density (microhard-
ness), roughness, composition, thickness, uniformity and
continuity. Table 2 presents the range of these charac-
teristics and those of the best coatings (based on a
statistical analysis of performance data).
Fig. 3a and b shows the surface morphology in plan
view and cross-section, respectively, of an EPP-cleaned
steel specimen. The observed topography is a direct
result of the interaction between physical processes
taking place during EPP. As noted earlier, a high
temperature plasma is created within the small size
hydrogen bubbles in the thin electrolyte layer on the

Table 1
Electrolytic plasma processing parameters used for cleaning and coating steel surfaces

Parameters Cleaning Zn coating I Zn coating II Zn – Al coating

Voltage (V) 170 – 200 180, 200, 220 180, 200 180, 200, 220
Current density (Aycm2) 0.23 – 0.45 0.11 – 0.78 0.3 – 0.5 0.8 – 1.2
Anode material Stainless steel Stainless steel Zn plate Stainless steel
Electrode gap (mm) 8, 12, 16 8, 12, 16 8, 12, 16 8, 10, 12
Electrolyte (wt.%) NaHCO3 ZnSO4 w20% ZnSO4q80% Al2(SO4)3x
14% 21%, 24%, 27% ZnSO4 24% 10%, 11.5%, 13%
Flow rate (lymin) 3 – 3.8 1.9 – 3.8 1.9 – 3.8 1.9 – 3.8
Temperature (8C) 75 73 73 70
Treatment time (s) 13 32 32 32
250 E.I. Meletis et al. / Surface and Coatings Technology 150 (2002) 246–256

Table 2
Characteristic data of the cleaned surfaces and coatings

Cleaned surface Zn coating I Zn coating II Zn – Al coatings

Thickness – 12 mm 15 mm 18 mm
Deposition rate – 0.37 0.47 0.56
(mmys) (0.28 – 0.53) (0.41 – 0.47) (0.41 – 0.56)
Roughness 2.5 mm 3.5 mm 2.5 mm 2.3 mm
(Ra) (1.8 – 3.4 mm) (2.2 – 8.2 mm) (1.5 – 2.5 mm) (0.8 – 3.8 mm)
Element content 1.38 wt.% O2 Zn Zn 3.0 at.% Al, Zn bal.
(1.38 – 7.3 wt.% O2) (0.2 – 3.0 at.% Al, Zn bal.)
Adhesion strength – )70 )70 )70
(MPa) (20 to )70) ()70) (30 to )70)
Hardness (GPa) 1.9 (bulk steel) 0.97 1.06 1.30
Note: Values in parentheses show the range of characteristic data determined for all samples treated under the parameters described in Table
1. Adhesion values )70 MPa show that failure occurred in the epoxy.

surface of the workpiece during EPP. This causes local-
ized melting but also shock waves from the collapsing
of the bubbles and thus, strong surface forces on small
molten patches of steel. The action of hydrogen is able
to reduce oxides present at the surface and results in a
clean surface. As the present experimental results show,
O content was reduced dramatically in all EPP-cleaned
specimens (Table 2). Typical EDAX spectra prior to
and after cleaning are shown in Fig. 4. Once the plasma
has dissipated, the temperature drops rapidly causing
freezing of the produced features on the surface. The
above processes leave an essentially ‘renewed’ surface,
which is virtually clean. The surface consists of force
impact craters and spheroidal projections at the rim of
the impact craters producing a highly desirable profile
for a subsequent coating treatment. In the present study,
the lowest O content was observed in the specimen
cleaned under the following EPP conditions: 12-mm
electrode gap, 170-V electrode voltage and 3.5 lymin
electrolyte flow rate.
Fig. 3c and d shows the morphology of the Zn coating
(Zn coating I) that exhibited the best characteristics.
This coating was developed by using an 8-mm electrode
gap, 200-V electrode voltage, 24% ZnSO4 solution and
3.6 lymin electrolyte flow rate. The coating exhibited
excellent adhesion ()70 MPa) and SEM observations
showed a dense and continuous structure with a thick-
ness of 12 mm with no discontinuities at the coatingy
substrate interface (Fig. 3d). It is interesting to note the
similarities in the surface morphology between the
cleaned steel surface (Fig. 3a), and the Zn coating (Fig.
3c). It is apparent that the plasmaysurface interactions
create similar effects during coating (i.e. localized melt-
ing) producing a very similar surface morphology.
Microhardness measurements at cross-sections of this
coating revealed high values (0.97 GPa) consistent with
SEM observations. Hardness of bulk Zn is approximate-
ly 0.8 GPA but in view of freezing expected after
localized melting during EPP, the coating grain size is
expected to be in the nanoscale (or even amorphous)
thus possessing a higher microhardness as observed
experimentally. Finally, the results show that surface
roughness can be controlled to a certain extent by the
processing parameters and that of the aforementioned
best coating was found to be approximately 3.6 mm.
The second type of Zn coating (Zn coating II) was
deposited by the same processing conditions as the
aforementioned Zn coating I but using a Zn anode
instead of a stainless steel anode. Compared to Zn
coating I, the best coating in this case exhibited a higher
deposition rate (0.47 mmys), a somewhat higher density
(microhardness, 1.06 GPa) and lower roughness (2.5
mm). Also, a relatively large but uniform grainycluster
structure was present on the surface (Fig. 3e). Obser-
vations at cross-sections also showed a dense and
uniform coating (Fig. 3f). It should be noted that when
a Zn anode is utilized during EPP, erosion of the anode
takes place under the electric field thus activating an
additional deposition mechanism. This is expected to
result in higher deposition rates, higher density and
smoother surfaces and is consistent with the experimen-
tal measurements of thickness, microhardness and rough-
ness. It is important to note that in both of these coating
treatments the deposition rates achieved are significantly
higher than those obtained by conventional electroplat-
ing processes.
Regarding the Zn–Al coatings, the WDS analysis
showed that under the EPP conditions used only small
amounts of Al could be incorporated into the coating.
The maximum Al content reached 3.0 at.%. This may
be considered significant in view of the fact that Al
deposition by conventional electroplating is not possible.
Surface and cross-section morphology of the best Zn–
Al coating obtained in the present study is presented in
Fig. 3g,h, respectively. This coating was developed
under a 12-mm electrode gap, 220-V electrode voltage,
10% electrolyte concentration and 2.9 lymin flow rate.
A uniform, large grainycluster was evident on the
 E.I. Meletis et al. / Surface and Coatings Technology 150 (2002) 246–256 251

Fig. 3. Surface (a, c, e and g) and cross-section (b, d, f and h) SEM micrographs of (a, b) the cleaned steel, (c, d) Zn coating I, (e, f) Zn coating
II and (g, h) Zn – Al coating, respectively.

surface. A high deposition rate was also achieved in this
case (0.56 mmys). The coating exhibited good conti-
nuity, with some voids due to the large cluster structure
as observed in the coating cross-section. Microhardness
measurements on coating cross-sections showed high
values indicative of high coating density. The micro-
hardness values obtained were significantly higher than
those observed in pure Zn. This more than likely is due
to solid solution strengthening effects.
For all of the Zn and Zn–Al coatings, the anchor
profile can be observed at the interface between the
coatings and steel substrates. SEM analysis also showed
that both Zn coatings were dense with good uniformity
and no voids present at the substrateycoating interface.
Closer observations showed that the Zn–Al coating
exhibited more irregularities on its top surface and some
voids in the coating structure. The reasons for such
differences in topography are not very clear at present.
However, the high electrode current density during the
Zn–Al coating treatment (Table 1) indicates that the
process is at the initial stage of U2 –U29 (Fig. 1), which
can lead to an unstable and weak plasma. The sintering
effects due to meltingycondensing in plasma discharge
channel on the Zn–Al coating are not as strong as those
252 E.I. Meletis et al. / Surface and Coatings Technology 150 (2002) 246–256

Fig. 4. EDAX spectra from the steel substrate (a) prior to and (b) after EPP cleaning.

during the Zn coating treatment. Thus, the Zn–Al
coating is expected to exhibit a larger cluster size. These
effects are under further investigation at present.
4.2. Characterization of EPP-cleaned outer surface
layer
In an effort to obtain more information on possible
metallurgical changes at the outermost surface region,
FIB and TEM studies were conducted on the cleaned
steel surfaces. A FIB cross-section into the surface of
EPP-cleaned specimens was made and high-resolution
imaging was obtained in secondary electron mode. Fig.
5a shows an overall view of the specimen surface and
cross-sectional area. It is evident that the bulk steel
structure has a relatively large grain size )10 mm
whereas the outer surface layer exhibits a very fine
grain structure. Fig. 5b is a high magnification image of
the nodule cross-section that is shown in the center
portion of Fig. 5a. Two very interesting observations
can be made. The bulk of the nodule exhibits a fine
grain structure with a size of approximately 0.5 mm. At
the surface of the nodule there is a thin layer with an
ultra-fine structure. This evidence strongly suggests that
quenching effects during freezing of locally melted
surface material produce a fine microstructure at the
surface layer. The grain structure at the latter outer
surface layer could not be resolved with secondary
electron imaging and thus it was further investigated by
high resolution TEM.
Thin foils were prepared from the cross-sectional area
of EPP-cleaned surfaces. The results showed the pres-
ence of a distinct outer surface layer that developed
after cleaning on the entire specimen surface (Fig. 6a).
 E.I. Meletis et al. / Surface and Coatings Technology 150 (2002) 246–256 253

Fig. 6. (a) Cross-section TEM image of the EPP-cleaned steel. (b)

Selected-area electron diffraction (SAED) pattern taken from the sur-
face layer of a thickness of approximately 150 nm showing a fine-
grained polycrystalline structure and (c) SAED pattern from the base
Fe showing the w311x zone diffraction pattern of bcc Fe.

4.3. Corrosion behavior

Fig. 8 presents the variation of the corrosion potential

of EPP-cleaned steel and background steel (cleaned by
mechanical grinding) as a function of time. Background
steel initially shows a small tendency for passivation
(increase in potential) but its potential is gradually
moving in the active direction and stabilizes at approx-

Fig. 5. FIB secondary electron image showing (a) overall morphology

of surface and cross-sectional area and (b) high magnification of the
nodule marked in (a) revealing a small grain structure in its interior
and an ultra-fine structured layer at its surface.

The thickness of the surface layer was found to vary

between 150 and 250 nm. Electron diffraction analysis
from the surface layer showed that it consists of an ultra
fine-grained structure (Fig. 6b), where the basic steel
contains the original large grain structure (Fig. 6c). High
resolution TEM showed that the grain size in that outer
layer is between 10 and 20 nm (Fig. 7). Plasma
discharge developing in the hydrogen bubbles at the
material surface during cleaning seems to have two
basic effects. Firstly it reduces andyor removes oxides
and mill scale from the surface and second, locally
melts the surface layer. Due to fast cooling rate of the Fig. 7. A representative high-resolution TEM image from the surface
thin molten surface layer a fine grain size develops. layer in Fig. 6a showing a polycrystalline structure. The grain size is
Thus, the end result is a clean, nanostructured surface. in the range of 10 – 20 nm in diameter.
254 E.I. Meletis et al. / Surface and Coatings Technology 150 (2002) 246–256

Fig. 8. Variation of corrosion potential of steel in tap water as a func-

tion of time.

imately y590 mV. On the contrary, the potential of the

EPP-cleaned steel is significantly higher than that of the
background steel during the entire testing period. Upon
exposure, the potential of the EPP-cleaned steel moves
in the noble (passive) direction at a relatively high rate
and stabilizes at approximately 50 mV (approx. 250 mV
higher than its initial potential). Also, a comparison
between the stabilized potentials (after 80=103 s) shows
that the EPP-cleaned steel has a potential that is approx-
imately 640 mV higher than that of the background
steel. These results indicate that the surface cleaned with
the EPP method exhibits passivation that remains stable
during the test duration while the plain steel tends to be
significantly more active. Visual examinations after test- Fig. 9. Anodic polarization behavior of steel in (a) tap water and (b)
ing were consistent with the above results since the 3.5% NaCl solution.
background steel surface was completely rusted where
the surface of the EPP-cleaned steel seemed intact.
During EPP treatment, hydrogen plasma develops at significantly lower (approx. 25 times lower) than that
high temperatures, and besides oxides is expected to exhibited by the background steel. These results are
also remove C from the steel structure. Thus, the present consistent with the presence of a pure iron layer at the
potential measurements are consistent with the formation surface of EPP-cleaned steel.
of a clean, pure iron surface layer (with no presence of The NaCl solution is an aggressive environment and
FeyC microgalvanic cells). the behavior in terms of corrosion rate, is similar for
Fig. 9 presents the anodic polarization behavior of both types of steel surfaces. However, the results show
steel in tap water and 3.5% NaCl solution and Table 3 that the corrosion potential difference remains at the
summarizes the corrosion properties calculated from same levels as in tap water indicating that even in the
these tests. Consistent with the previous results in tap
water, the EPP-cleaned steel exhibited a more noble Table 3
corrosion potential and passivated for the entire potential Summary of corrosion properties of steel from anodic polarization
testing
range tested. On the contrary, the background steel
exhibited breakdown at a potential of approximately 170 Materialycondition Corrosion potential Corrosion rate
mV. It should be noted that at even lower potentials, the mV (SCE) mAycm2
background steel exhibits a more active behavior (higher Tap water NaCl sol. Tap water NaCl sol.
corrosion current density) compared to EPP-cleaned
steel. Also, the results show that the corrosion rate Background steel y325 y535 3.51 11.8
EPP-cleaned steel y196 y385 0.14 9.5
exhibited by the EPP cleaned steel in tap water is
 E.I. Meletis et al. / Surface and Coatings Technology 150 (2002) 246–256
Fig. 10. Anodic polarization behavior of various coatings in (a) tap
water and (b) 3.5% NaCl solution.
NaCl solution, the EPP-cleaned steel surface is thermo-
dynamically more stable than the background steel.
Fig. 10 presents the anodic polarization behavior of
the EPP Zn and Zn–Al coatings and the hot dip
galvanized coating in tap water and 3.5% NaCl solution.
In tap water, all three coatings exhibit activation polar-
ization and comparable corrosion rates with the EPP
coatings possessing a little higher corrosion potential.
The behavior in NaCl solution is along the same lines
with the EPP coatings exhibiting somewhat higher
corrosion potential. Again all three coatings show acti-
vation polarization at potentials close to the OCP. The
hot dip galvanized coating exhibited a little lower
corrosion rate that can probably be attributed to the
particular surface topography of the EPP coatings. The
presence of craters or discontinuities at the surface
produced a larger surface area than the nominal area
used to estimate the current density and therefore the
actual corrosion current density may be smaller. Thus,
the present results demonstrate that the EPP method is
capable of producing sacrificial coatings for corrosion
255
protection while at the same time produces a ‘passive’
steel outer surface that can serve as an additional
corrosion resistance layer.
5. Conclusions
The results showed that EPP can effectively clean
steel surfaces that possess highly desirable anchor pro-
files. The produced surfaces are nanocrystalline and
exhibit a passive behavior. The latter is a direct outcome
of the physics involved in the cleaning process and
results in a significantly improved corrosion resistance
compared to base steel. This feature of enhanced lon-
gevity of the cleaned surface is important when consid-
ering the quality of subsequent coating operations and
the allowable time lag prior to coating. The EPP method
is also capable of producing adherent, dense and uniform
Zn and Zn–Al coatings that can function as sacrificial
anodes protecting the underlying steel while the passive
steel outer surface layer can provide an additional
corrosion resistance mechanism. The present results
show that EPP is an emerging, high potential cleaning
and coating technology.
Acknowledgements
Financial support for this work was provided by the
Louisiana Transportation Research Center and Depart-
ment of Transportation (Award No. DTFH 61-00-X-
00008). The authors would like to thank Mr Edward
Daigle (Metals Technology Inc.) for assisting with the
electrolytic plasma treatments and Dr Michael Phaneuf
(Fibics Corp.) for conducting the FIB work.
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